CN116598472A - Doped positive electrode material, synthesis method and application thereof in sodium ion battery - Google Patents

Doped positive electrode material, synthesis method and application thereof in sodium ion battery Download PDF

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CN116598472A
CN116598472A CN202310659352.7A CN202310659352A CN116598472A CN 116598472 A CN116598472 A CN 116598472A CN 202310659352 A CN202310659352 A CN 202310659352A CN 116598472 A CN116598472 A CN 116598472A
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layered
doped
positive electrode
doping
sodium
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潘斌
董栋
于圣明
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Zhejiang Yuna Technology Co ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
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    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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Abstract

The invention discloses a doped anode material, a synthesis method and application thereof in sodium ion batteries, wherein the material is an O3 phase layered material with a chemical general formula of Na n [Mn 1‑x‑y‑z T1 x T2 y T3 z ]O 2‑δ (X d O m ) δ Wherein T1 is at least one of Cu, fe, ni, cr, co, T2 is at least one of Li and Mg, T3 is at least one of rare earth La, ce, pr, nd, and XO m Is PO (PO) 4 3‑ 、P 2 O 7 4‑ 、BO 3 3‑ 、BO 4 5‑ 、SiO 4 4‑ 、SiO 3 2‑ 、Si 2 O 5 2‑ At least one of them. The manganese-based layered material in the invention is prepared by uniformly doping active element T1 and inactive element T2, and rare earth element T3 and polyanion X d O m The co-doping of the material and the synergistic effect of the doping elements and the doping groups can effectively inhibit adverse phase change of the material in the charge-discharge process, improve the stability of the material in electrolyte and air, and the obtained material has high capacity, excellent multiplying power performance and long cycle life.

Description

Doped positive electrode material, synthesis method and application thereof in sodium ion battery
Technical Field
The invention relates to the field of novel sustainable energy storage batteries, in particular to a doped positive electrode material, a synthesis method and application thereof in sodium ion batteries.
Background
Development of sustainable clean energy sources such as wind energy, solar energy and tidal energy is an urgent need, but the clean energy sources show intermittent and wavy properties along with weather and climate change, and corresponding energy storage batteries are needed, so that the clean energy sources are provided with an energy storage mode, which is the development direction of new energy sources. In the existing energy storage batteries, lithium ion batteries are mainstream, but with rapid expansion of the installed capacity of energy storage, lithium resources are consumed too fast, long-term development faces resource problems and potential safety hazards, and sodium ion batteries have comprehensive advantages of good safety, low cost, abundant resources, environmental friendliness and the like, and are suitable for large-scale energy storage.
Sodium ion batteries have the advantages of good reproducibility, low cost, high capacity, and the like. However, sodium ion batteries are still under investigation in the early stages, requiring more work to improve their performance. One of the key issues is the choice of cathode material. The positive electrode material is one of the most important components in the battery, and can affect the performance of the battery in sodium ion batteries, and the positive electrode material is required to have high electrochemical reactivity, good conductivity and stable cycle performance. Currently, the positive electrode materials of sodium ion batteries mainly include oxides, phosphates, sulfides, and the like.
For the development of sodium ion batteries, the selection of the appropriate cathode material is a key factor. The layered oxide has the advantages of high capacity, good multiplying power performance, long cycle life and the like, and is suitable for the positive electrode of the sodium ion battery. Sodium-based layered oxides have more phases and more complex compositions than lithium ion battery layered oxides. In addition, sodium-based layered oxides are more prone to lattice loss of oxygen and are subject to decomposition by moisture in air than lithium-ion layered oxides. Therefore, such materials undergo complex phase changes during cycling, resulting in distortion of the crystal lattice and oxygen evolution, which leads to deterioration of the cycling performance.
Disclosure of Invention
The invention aims at the problems and discloses a doped layered material with stable structure, which has an O3 phase structure and is used as the positive electrode of a sodium ion battery. In the material, naMnO is used 2 The Mn side doping and the O side are combined to effectively inhibit adverse phase change in the charge-discharge process, stabilize crystal lattices, and improve stability of the material in electrolyte and air, so that specific capacity, rate capability and cycle life of the material are balanced.
The doped layered anode has a chemical general formula of Na n [Mn 1-x-y-z T1 x T2 y T3 z ]O 2-δ (X d O m ) δ Wherein T1 is at least one of Cu, fe, ni, cr, co, T2 is at least one of Li and Mg, T3 is at least one of light rare earth La, ce, pr, nd, and X d O m Is PO (PO) 4 3- 、P 2 O 7 4- 、BO 3 3- 、BO 4 5- 、SiO 4 4- 、SiO 3 2- 、Si 2 O 5 2- Wherein x is more than or equal to 0.2 and less than or equal to 0.7,0<y is not less than 0.1,0.005, z is not less than 0.05, delta is not less than 0.005, n is not less than 0.05,0.85, n is not less than 1, and the value of x, y, z, n and delta accords with the electric neutrality principle.
In the above formula, mn, ti, T2, T3 are located in the transition metal layer of the O3 phase crystal, X d O m Located at the O-position.
The doping element T1 is an electrochemical active element, and the electrochemical activity refers to that the element can contribute to capacity through valence change in the charge and discharge process; the doping element T2 is an electrochemical inert element, and the electrochemical inert element means that the element cannot contribute to capacity through valence change in the charge and discharge process; the electric neutrality principle refers to n+ (1-x-y-z) xn1+xn2+yxn3+zxn4= (2-delta) x2+delta xN5, wherein N1, N2, N3, N4, N5 are the valencies of the elements Mn, T1, T2, T3 and the radical X, respectively d O m Absolute value of valence.
In the doped layered material Na n [Mn 1-x-y-z T1 x T2 y T3 z ]O 2-δ (X d O m ) δ Preferably, the active element T1 is at least one selected from Cu, fe, ni, cr, co; preferably, 0.2.ltoreq.x.ltoreq.0.7, in which the product is susceptible to O3 phase formation and the capacity, operating voltage and cycle life reach equilibrium.
In the doped layered material Na n [Mn 1-x-y-z T1 x T2 y T3 z ]O 2-δ (X d O m ) δ Preferably, the inert element T2 is at least one selected from Li and Mg. The advantages of this type of metal doping are: (1) Easy to be matched with O and X in crystal lattice d O m Forming an ionic bond to promote the formation of O3 phase; (2) The ion radius is larger, so that lattice distortion caused by the decrease of the ion radius when the active metal T1 is charged can be compensated, the slippage of the transition metal layer is restrained, and adverse phase change is restrained; (3) Facilitating Mn to reach the most stable tetravalent state so as to inhibit Mn 3+ John-Teller effect of (a) and increase Na content to increase capacity; (4) Is favorable for activating the oxidation-reduction reaction of T1, thereby promoting the deintercalation of sodium ions and improving the capacity. Preferably, 0<y is less than or equal to 0.1, and more preferably, y is less than or equal to 0.02 and less than or equal to 0.08, and within the range, the capacity, the working voltage and the cycle life can be balanced.
In the doped layered material Na n [Mn 1-x-y-z T1 x T2 y T3 z ]O 2-δ (X d O m ) δ In (2), rare earth element T3 doping is performed, and preferably, the rare earth element is at least one of light rare earth elements La, ce, pr, nd, and the effect of rare earth element T3 doping is as follows: (1) The support is used, the radius of the rare earth element T3 is unchanged, and the lattice distortion of the transition metal layer of the element T1 rechargeable battery is restrained; (2) The rare earth metal has special f electron, can interact with d electron of T2 to change energy band structure so as to promote oxidation/reduction reaction of T1 and sodiumIs removed from the mold; (3) Is beneficial to improving the stability of the material in the air and the electrolyte. Preferably, z is 0.005.ltoreq.z.ltoreq.0.05, and in this range, the specific capacity, cycle life and rate performance can be balanced.
In the doped layered material Na n [Mn 1-x-y-z T1 x T2 y T3 z ]O 2-δ (X d O m ) δ In the above, it is preferable to carry out the oxygen position X d O m Doping, X d O m The effect of doping is: (1) Stabilizing the crystal structure, and inhibiting oxygen evolution and unfavorable phase change during charge and discharge; (2) The stability of the material in the air and the stability of the material in the electrolyte are improved; (3) Promote oxidation/reduction reaction of T1 and intercalation and deintercalation of sodium, and improve capacity. Preferably, delta is not less than 0.005 and not more than 0.05, and within the range, the specific capacity, the cycle life and the multiplying power performance can be balanced.
In the doped layered material Na n [Mn 1-x-y-z T1 x T2 y T3 z ]O 2-δ (X d O m ) δ Preferably, n is more than or equal to 0.85 and less than or equal to 1, the doped layered material presents O3 phase, elements Mn, T1, T2 and T3 in the transition metal layer are orderly distributed and uniformly dispersed in the lattice transition metal layer, and X d O m The groups are uniformly dispersed at the O position of the crystal lattice, and through the synergistic effect between the groups, the adverse phase change of the material in the charge and discharge process is inhibited, oxygen evolution is inhibited, and the stability of the material in air and electrolyte is improved, so that the electrochemical performance of the material is improved.
The invention also discloses a preparation method of the doped layered material, which comprises a solid phase reaction method, a coprecipitation method, a spray drying method and a sol-gel method. In the coprecipitation method, the spray drying method and the sol-gel method, only a precursor is generally obtained, and a final product is obtained through a solid phase reaction.
In the synthesis, in order to compensate sodium burning loss during high-temperature reaction, the sodium is excessive by 1% -10%.
Preferably, the Na n [Mn 1-x-y-z T1 x T2 y T3 z ]O 2-δ (X d O m ) δ The particle size of the electrode is 0.1-20 microns, and in the particle size range, the compaction density of the electrode is improved, and the processability of the electrode is improved.
The invention discloses an electrode containing the doped lamellar material, which is used as a positive electrode of a sodium ion battery and consists of a doped lamellar active material, conductive carbon and a polymer binder. Preferably, the conductive carbon is at least one selected from the group consisting of carbon nanotubes, acetylene black, graphene and carbon fibers; preferably, the polymer binder is a polyfluorinated olefin, and is at least one selected from polyvinylidene fluoride, polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene and polyfluoroperfluoroethylene.
Preferably, a sodium supplement is added into the doped layered active material, wherein the sodium supplement comprises Na 4 SiO 4 The conductive agent is selected from at least one of acetylene black, carbon nano tubes, carbon fibers and graphene, and the catalyst is transition metal oxide selected from MnO 2 、CuO、Mn 3 O 4 At least one of NiO and Na 4 SiO 4 The weight ratio of the conductive agent to the catalyst is 1:0.01-0.1:0.01-0.1; preferably, the weight ratio of the sodium supplementing agent to the layered active material is 1:100-10:100, and sodium loss at the anode during primary charging can be effectively compensated by sodium supplementing, so that primary coulombic efficiency is improved.
The invention also discloses a preparation method of the layered positive electrode material for the sodium ion battery, and an organic sodium ion battery using the doped layered positive electrode is obtained.
Preferably, the layered positive electrode material, metallic sodium as a negative electrode, glass fiber as a diaphragm, 1M NaPF 6 Propylene carbonate/methyl ethyl carbonate solution as electrolyte, and adding 4% of fluorinated ethylene carbonate by weight of the electrolyte, and assemblingA button cell. Preferably, the organic solvent is at least one selected from, but not limited to, methyl ethyl carbonate, propylene carbonate, ethylene carbonate, diethyl carbonate and dimethyl carbonate.
Preferably, the sodium salt is at least one selected from sodium perchlorate, sodium hexafluorophosphate, sodium bisoxalato borate, sodium bistrifluoromethane sulfonyl imide, sodium tetrafluoroborate, sodium trifluoromethane sulfonate and sodium bisfluoro sulfonyl imide.
Compared with the prior art, the invention has the following advantages:
1. the doped layered positive electrode material prepared by the invention is prepared by co-doping active and inert elements in bulk phase, in particular oxygen side X d O m Synergistic effect of group doping and manganese-side rare earth element doping, i.e. X d O m The group and rare earth element generate lattice coordination effect, change the crystal energy band structure, promote the formation of O3 phase, effectively inhibit the occurrence of lattice distortion, unfavorable phase change and oxygen evolution, improve the stability of the material in air and electrolyte, and balance the capacity, the multiplying power performance and the cycle life.
2. The doped layered anode material prepared by the simple method has the advantages of simple and controllable process, low cost, short period, low energy consumption, suitability for industrial production and the like.
Drawings
FIG. 1 is an X-ray diffraction pattern (XRD) of the doped layered cathode material prepared in example 1;
FIG. 2 is a charge-discharge curve of the doped layered cathode material prepared in example 1;
fig. 3 is a cycle life chart of the doped layered cathode material prepared in example 1.
Detailed Description
Example 1
According to Na 0.91 [Mn 0.44 Fe 0.24 Ni 0.26 Li 0.04 La 0.02 ]O 1.99 (BO 3 ) 0.01 Stoichiometric ratio, the material was prepared using a solid phase firing process.
Stoichiometric in volumeRatio of Na 2 CO 3 ，MnO 2 、Fe 2 O 3 、NiO、Li 2 CO 3 、La 2 O 3 、H 3 BO 3 And mixing uniformly, ball milling to obtain a precursor, wherein the ball milling time is 15 hours, the rotating speed is 350rpm, placing the precursor in a muffle furnace, and roasting at 810 ℃ in the air for 15 hours to obtain the doped layered material.
The product was analyzed by XRD to be O3 phase, see FIG. 1. The material prepared in this example was used as the positive electrode, sodium metal as the negative electrode, glass fiber as the separator, and 1M NaPF 6 The Propylene Carbonate (PC)/methyl ethyl carbonate (EMC) solution is taken as electrolyte, fluorinated Ethylene Carbonate (FEC) accounting for 4 percent of the weight of the electrolyte is added, a button cell is assembled, a charge-discharge test is carried out, the current density is 15mA/g, the voltage range is 2-4V, the charge-discharge curve is shown in figure 2, the specific capacity is 129mAh/g, and the capacity retention rate of the material is 87.0 percent after 100 cycles under the current density of 150mA/g, which is shown in figure 3.
Comparative example 1
The material was prepared as in example 1, except that La doping was not performed during the preparation, and La was partially replaced with Ni, i.e., la in the raw material 2 O 3 Substitution with NiO, ni increased in molar amount equivalent to La in example 1, to give Na 0.93 [Mn 0.44 Fe 0.24 Ni 0.28 Li 0.04 ]O 1.99 (BO 3 ) 0.01 . Under the same test conditions as in example 1, the capacity retention was 81.4% over 100 cycles.
Comparative example 2
The materials were prepared as in example 1, except that BO was not incorporated during the preparation 3 3- I.e. without the use of H 3 BO 3 Precursor, BO in lattice 3 Substituted by O to give Na 0.90 [Mn 0.44 Fe 0.24 Ni 0.26 Li 0.04 La 0.02 ]O 2 . Under the same test conditions as in example 1, the capacity retention was 80.7% over 100 cycles.
Comparative example 3
The materials were prepared as in example 1, except that La and BO were not incorporated during the preparation 3 3- The La part being replaced by Ni, i.e. La in the starting material 2 O 3 Replaced by NiO, the molar amount of Ni increase was equal to that of La in example 1, and H was not used 3 BO 3 Precursor, BO in lattice 3 Substituted by O to give Na 0.92 [Mn 0.44 Fe 0.24 Ni 0.28 Li 0.04 ]O 2 . Under the same test conditions as in example 1, the capacity retention was 75.3% over 100 cycles.
Comparative example 4
The materials were prepared as in example 1, except that BO was not incorporated during the preparation 3 3- BO-doped 3 3- Partly by F - Substitution, i.e. without the use of H 3 BO 3 Precursor, using NH 4 F precursor, BO in lattice 3 Substituted by F to give Na 0.89 [Mn 0.44 Fe 0.24 Ni 0.26 Li 0.04 La 0.02 ]O 1.99 F 0.01 . Under the same test conditions as in example 1, the capacity retention was 83.7% over 100 cycles.
Example 2
According to Na 0.90 [Mn 0.44 Fe 0.24 Ni 0.26 Li 0.04 La 0.02 ]O 1.995 (BO 3 ) 0.005 Stoichiometric ratio, the material is prepared by combining a coprecipitation method with solid phase roasting.
Stoichiometric ratio of NiSO 4 、MnSO 4 、FeSO 4 Placing the mixture in deionized water, uniformly mixing to obtain a salt solution with the total concentration of 2mol/L, preparing an ammonia water solution with the concentration of 1mol/L and a NaOH solution with the concentration of 4mol/L as a complexing agent and a precipitating agent respectively, then simultaneously injecting the salt solution, the complexing agent and the precipitating agent into a reaction container, performing coprecipitation reaction, setting the coprecipitation reaction temperature to 60 ℃, and adjusting the flow rate of the NaOH solution to control the pH value to be 11.0. Centrifuging and drying the obtained precipitate, and mixing with Na 2 CO 3 、Li 2 CO 3 、La 2 O 3 、H 3 BO 3 Mixing according to the metering ratio, then placing in a muffle furnace, and roasting for 12 hours at 830 ℃ in the air atmosphere to obtain the doped layered material.
The product was analyzed by XRD to be O3 phase. The material prepared in this example was used as the positive electrode, sodium metal as the negative electrode, glass fiber as the separator, and 1M NaPF 6 The PC/EMC solution is taken as electrolyte, and FEC with the weight of 4 percent of the electrolyte is added, a button cell is assembled, charge and discharge tests are carried out, the current density is 150mA/g, the voltage range is 2-4V, and the capacity retention rate is 85.5 percent after 100 times of circulation.
Example 3
According to Na 0.92 [Mn 0.44 Fe 0.24 Ni 0.26 Li 0.04 La 0.02 ]O 1.98 (BO 3 ) 0.02 Stoichiometric ratio, the material was prepared using a solid phase firing process.
Stoichiometric ratio of Na 2 CO 3 ，MnO 2 、Fe 2 O 3 、NiO、Li 2 CO 3 、La 2 O 3 、H 3 BO 3 And mixing uniformly, ball milling to obtain a precursor, wherein the ball milling time is 15 hours, the rotating speed is 350rpm, placing the precursor in a muffle furnace, and roasting at 810 ℃ in the air for 15 hours to obtain the doped layered material.
The product was analyzed by XRD to be O3 phase. The material prepared in this example was used as the positive electrode, sodium metal as the negative electrode, glass fiber as the separator, and 1M NaPF 6 The PC/EMC solution is taken as electrolyte, and FEC with the weight of 4 percent of the electrolyte is added, a button cell is assembled, charge and discharge tests are carried out, the current density is 150mA/g, the voltage range is 2-4V, and the capacity retention rate of the material is 85.1 percent after 100 times of circulation.
Example 4
According to Na 0.91 [Mn 0.44 Fe 0.24 Ni 0.26 Li 0.04 La 0.01 Ce 0.01 ]O 1.99 (BO 3 ) 0.01 Stoichiometric ratio, the material is prepared by combining a sol-gel method with solid phase roasting.
Stoichiometric ratio of NaNO 3 ，LiNO 3 、Mn(NO 3 ) 2 、Ni(NO 3 ) 2 、Fe(NO 3 ) 3 、La(NO 3 ) 3 、Ce(NO 3 ) 3 、H 3 BO 3 Mixing the materials in deionized water, stirring to obtain sol, adding citric acid, stirring at 70deg.C to obtain gel, placing in a muffle furnace, and calcining at 820 deg.C in air for 15 hr to obtain doped layered material.
The product was analyzed by XRD with O3 phase. The material prepared in this example was used as the positive electrode, sodium metal as the negative electrode, glass fiber as the separator, and 1M NaPF 6 The PC/EMC solution is taken as electrolyte, and FEC with the weight of 4 percent of the electrolyte is added, a button cell is assembled, charge and discharge tests are carried out, the current density is 150mA/g, the voltage range is 2-4V, and the capacity retention rate is 87.8 percent after 100 times of circulation.
Example 5
According to Na 0.91 [Mn 0.44 Fe 0.24 Ni 0.26 Li 0.04 Ce 0.02 ]O 1.99 (BO 3 ) 0.01 Stoichiometric ratio, the material was prepared using a solid phase method.
Stoichiometric ratio of Na 2 CO 3 ，MnO 2 、Fe 2 O 3 、NiO、LiOH、Ce(NO 3 ) 3 And H 3 BO 3 And (3) uniformly mixing, ball milling in acetone to obtain a precursor, wherein the ball milling time is 15 hours, the rotating speed is 350rpm, placing the precursor in a muffle furnace, and roasting at 820 ℃ in an air atmosphere for 15 hours to obtain the doped layered material.
The material prepared in this example was used as the positive electrode, sodium metal as the negative electrode, glass fiber as the separator, and 1M NaPF 6 The PC/EMC solution is taken as electrolyte, and FEC with the weight of 4 percent of the electrolyte is added, a button cell is assembled, charge and discharge tests are carried out, the current density is 150mA/g, the voltage range is 2-4V, and the capacity retention rate is 85.8 percent after 100 times of circulation.
Example 6
According to Na 0.91 [Mn 0.44 Fe 0.24 Ni 0.26 Li 0.04 La 0.02 ]O 1.99 (PO 4 ) 0.01 Stoichiometric ratio, the material is prepared by adopting a coprecipitation method and matching with solid phase reaction.
Stoichiometric ratio of NiSO 4 、MnSO 4 、FeSO 4 Placing the mixture in deionized water, uniformly mixing to obtain a salt solution with the total concentration of 2mol/L, preparing an ammonia water solution with the concentration of 1mol/L and a NaOH solution with the concentration of 4mol/L as a complexing agent and a precipitating agent respectively, then simultaneously injecting the salt solution, the complexing agent and the precipitating agent into a reaction container for coprecipitation reaction, controlling the pH value to be 11.0 by adjusting the flow rate of the NaOH solution at the coprecipitation reaction temperature of 50 ℃.
Centrifuging and drying the obtained precipitate, and mixing with Na 2 CO 3 And Li (lithium) 2 CO 3 、La 2 O 3 、NH 4 H 2 PO 4 Mixing according to the metering ratio, then placing in a muffle furnace, and roasting for 15 hours at 820 ℃ in the air atmosphere to obtain the doped layered material.
The material prepared in this example was used as the positive electrode, sodium metal as the negative electrode, glass fiber as the separator, and 1M NaPF 6 The PC/EMC solution is taken as electrolyte, and FEC with the weight of 4 percent of the electrolyte is added, a button cell is assembled, charge and discharge tests are carried out, the current density is 150mA/g, the voltage range is 2-4V, and the capacity retention rate is 89.0 percent after 100 times of circulation.
Example 7
According to Na 0.87 [Mn 0.44 Fe 0.24 Ni 0.26 Mg 0.04 La 0.02 ]O 1.99 (PO 4 ) 0.01 Stoichiometric ratio, the material was prepared using a solid phase method.
Stoichiometric ratio of NaNO 3 ，Mn 2 O 3 、Fe 2 O 3 、NiO、MgO、La 2 O 3 And NH 4 H 2 PO 4 Uniformly mixing, taking deionized water as a medium, and performing sanding to obtain precursor slurry, wherein the sanding time is 4 hours, the rotating speed is 1800rpm, and performing spray drying on the sanded slurry to obtain a precursor, wherein the inlet temperature of a spray dryer is 180 ℃, and the outlet of the spray dryer isAnd (3) placing the precursor in a muffle furnace at 110 ℃, and roasting at 820 ℃ in an air atmosphere for 15 hours to obtain the doped layered material.
The material prepared in this example was used as the positive electrode, sodium metal as the negative electrode, glass fiber as the separator, and 1M NaPF 6 The PC/EMC solution is taken as electrolyte, and FEC with the weight of 4 percent of the electrolyte is added, a button cell is assembled, charge and discharge tests are carried out, the current density is 150mA/g, the voltage range is 2-4V, and the capacity retention rate is 87.6 percent after 100 times of circulation.
Example 8
According to Na 0.91 [Mn 0.42 Fe 0.30 Ni 0.20 Li 0.06 La 0.02 ]O 1.99 (PO 4 ) 0.01 Stoichiometric ratio, the material is prepared by combining a coprecipitation method with solid phase roasting.
Stoichiometric ratio of MnSO 4 、FeSO 4 、NiSO 4 Stirring uniformly in deionized water to obtain a salt solution with the total concentration of 1mol/L, preparing an ammonia water solution with the total concentration of 0.5mol/L and a NaOH solution with the total concentration of 2mol/L as a complexing agent and a precipitating agent respectively, then simultaneously injecting the salt solution, the complexing agent and the precipitating agent into a reaction container for coprecipitation reaction, wherein the coprecipitation reaction temperature is 60 ℃, and controlling the pH value to be 11.0 by adjusting the flow rate of the NaOH solution. Centrifuging and drying the obtained precipitate, and mixing with Na 2 CO 3 、Li 2 CO 3 、La 2 O 3 、NH 4 H 2 PO 4 Mixing according to the metering ratio, then placing in a muffle furnace, and roasting for 10 hours at 840 ℃ in the air atmosphere to obtain the doped layered material.
The product was analyzed by XRD to be O3 phase. The material prepared in this example was used as the positive electrode, sodium metal as the negative electrode, glass fiber as the separator, and 1M NaPF 6 The PC/EMC solution is taken as electrolyte, and FEC with the weight of 4 percent of the electrolyte is added, a button cell is assembled, charge and discharge tests are carried out, the current density is 150mA/g, the voltage range is 2-4V, and the capacity retention rate is 91.2 percent after 100 times of circulation.
Example 9
According to Na 0.91 [Mn 0.42 Fe 0.30 Ni 0.16 Cu 0.04 Li 0.06 La 0.02 ]O 1.99 (PO 4 ) 0.01 Stoichiometric ratio, the material was prepared using a solid phase method. Stoichiometric ratio of NaNO 3 ，Mn 3 O 4 、Ni(OH) 2 、Fe 3 O 4 、CuO、LiOH、La 2 O 3 、NH 4 H 2 PO 4 And mixing uniformly, ball milling to obtain a precursor, wherein the ball milling time is 15 hours, the rotating speed is 350rpm, placing the precursor in a muffle furnace, and roasting at 830 ℃ in an air atmosphere for 15 hours to obtain the doped layered material. The material prepared in this example was used as the positive electrode, sodium metal as the negative electrode, glass fiber as the separator, and 1M NaPF 6 The PC/EMC solution is taken as electrolyte, and FEC with the weight of 4 percent of the electrolyte is added, a button cell is assembled, charge and discharge tests are carried out, the current density is 150mA/g, the voltage range is 2-4V, and the capacity retention rate is 92.4 percent after 100 times of circulation.
Example 10
According to Na 0.89 [Mn 0.42 Fe 0.30 Ni 0.16 Cu 0.04 Mg 0.02 Li 0.04 La 0.02 ]O 1.99 (PO 4 ) 0.01 Stoichiometric ratios, the material was prepared using spray drying. Stoichiometric ratio of NaNO 3 ，Mn(NO 3 ) 2 、Fe(NO 3 ) 3 、Ni(NO 3 ) 2 、Cu(NO 3 ) 2 、Mg(NO 3 ) 2 、La(NO 3 ) 3 、LiNO 3 、NH 4 H 2 PO 4 Mixing the materials in deionized water, fully stirring the materials to obtain a mixed solution, and spray-drying the mixed solution to obtain a precursor, wherein the inlet temperature of a spray-dryer is 180 ℃, the outlet temperature of the spray-dryer is 110 ℃, and then placing the obtained precursor in a muffle furnace, and roasting the obtained precursor in an air atmosphere at 820 ℃ for 15 hours to obtain the doped layered material. The material prepared in this example was used as the positive electrode, sodium metal as the negative electrode, glass fiber as the separator, and 1M NaPF 6 The PC/EMC solution of (2) is taken as electrolyte, and FEC accounting for 4 percent of the weight of the electrolyte is added, and a button cell is assembled for carrying outAnd the charge and discharge test shows that the current density is 150mA/g, the voltage range is 2-4V, and the capacity retention rate is 93.1% after 100 times of circulation.
Table 1 performance comparison
As can be seen from Table 1 above, examples 1 to 10 prepared by the present invention have better properties and capacity retention up to 93.1% than the layered materials of comparative examples 1 to 4. As shown by comparison of examples 1 to 10, when the element T1 is doped with Ni, fe and Cu, the element T2 is doped with Li and Mg, the element T3 is doped with La, and the polyanion is doped with PO 4 3- Doped with Na 0.89 [Mn 0.42 Fe 0.30 Ni 0.16 Cu 0.04 Mg 0.02 Li 0.04 La 0.02 ]O 1.99 (PO 4 ) 0.01 The material prepared by the stoichiometric ratio has better performance, and the capacity retention rate reaches 93.1 percent.
From the comparison of examples 1 to 3, the cycling stability of the materials is better at the appropriate polyanion content, and from the comparison of examples 1 to 3 and examples 6 to 10, PO 4 3- The doping effect is better than BO 3 3- The obtained material has better cycle stability, the comparison of examples 1, 4 and 5 shows that the doping effect of rare earth La is better than Ce, but La and Ce co-doping has better synergistic effect, namely f electrons of the La and the Ce interact, the energy band structure of the crystal is changed, the comparison of examples 6 and 8-10 shows that the doping amount of Fe and Li is improved, the doping amount of Ni is reduced, the content of Mn is properly reduced, the cycle performance of the material is improved, and the comparison of examples 6, 7 and 10 shows that Li doping is better than Mg doping, but Li and Mg co-doping are more beneficial to improving the cycle stability due to the synergistic effect of the two.
Variations and modifications of the above-described embodiments will occur to those skilled in the art upon reading and understanding the foregoing description. Therefore, the present invention is not limited to the above-described embodiments, but is intended to be capable of modification, substitution or variation in light thereof, which will be apparent to those skilled in the art in view of the present invention.

Claims (6)

1. A doped layered anode material is characterized in that: the layered positive electrode material is subjected to cation doping and polyanion doping at the same time, and the doped cations are positioned in the transition metal layer; the chemical general formula of the layered anode is Na n [Mn 1-x-y-z T1 x T2 y T3 z ]O 2-δ (X d O m ) δ Wherein T1 is at least one of Cu, fe, ni, cr, co, T2 is at least one of Li and Mg, T3 is at least one of rare earth La, ce, pr, nd, and X d O m Is PO (PO) 4 3- 、P 2 O 7 4- 、BO 3 3- 、BO 4 5- 、SiO 4 4- 、SiO 3 2- 、Si 2 O 5 2- Wherein x is more than or equal to 0.2 and less than or equal to 0.7,0<y is not less than 0.1,0.005, z is not less than 0.05, delta is not less than 0.005, n is not less than 0.05,0.85, n is not less than 1, and the value of x, y, z, n and delta accords with the electric neutrality principle.
2. The doped layered cathode material of claim 1, wherein: the layered positive electrode presents O3 phase, elements Mn, T1, T2 and T3 are uniformly dispersed in the whole crystal lattice, and polyanion X d O m Uniformly dispersed in the whole crystal lattice, wherein Mn, ti, T2 and T3 are positioned in a transition metal layer of O3 phase crystal, X d O m Located at the O-position.
3. The method for preparing a doped layered cathode material according to claim 1 or 2, characterized in that: the layered anode material is synthesized by one or more of a solid phase method, a sol-gel method, a coprecipitation method or a spray drying method.
4. The method for preparing a doped layered cathode material according to claim 3, wherein: the dosage of sodium in the preparation process is 1% -10%.
5. Use of the doped layered cathode material according to any one of claims 1-2, characterized in that: the layered positive electrode material is used for preparing sodium ion batteries.
6. The use of a doped layered cathode material according to claim 5, wherein: the layered positive electrode material, sodium metal as negative electrode, glass fiber as diaphragm, 1M NaPF 6 The propylene carbonate/methyl ethyl carbonate solution is taken as electrolyte, and fluorinated ethylene carbonate accounting for 4 percent of the weight of the electrolyte is added to assemble the button cell.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116750802A (en) * 2023-08-21 2023-09-15 中节能万润股份有限公司 Preparation method and application of layered oxide sodium ion battery positive electrode material

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN116750802A (en) * 2023-08-21 2023-09-15 中节能万润股份有限公司 Preparation method and application of layered oxide sodium ion battery positive electrode material

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